DE19730085A1 - Ether carboxylic acids as asphaltene dispersants in crude oils - Google Patents

Ether carboxylic acids as asphaltene dispersants in crude oils

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Publication number
DE19730085A1
DE19730085A1 DE19730085A DE19730085A DE19730085A1 DE 19730085 A1 DE19730085 A1 DE 19730085A1 DE 19730085 A DE19730085 A DE 19730085A DE 19730085 A DE19730085 A DE 19730085A DE 19730085 A1 DE19730085 A1 DE 19730085A1
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Germany
Prior art keywords
ether carboxylic
crude oils
carboxylic acids
asphaltenes
dispersants
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DE19730085A
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German (de)
Inventor
Dennis Dr Miller
Axel Vollmer
Michael Dr Feustel
Peter Dr Klug
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Priority to DE19730085A priority Critical patent/DE19730085A1/en
Priority to CN98807194A priority patent/CN1263581A/en
Priority to EP98939618A priority patent/EP0995012B1/en
Priority to IDW20000011A priority patent/ID24250A/en
Priority to BR9811691-6A priority patent/BR9811691A/en
Priority to PCT/EP1998/004158 priority patent/WO1999004138A1/en
Priority to DE59800567T priority patent/DE59800567D1/en
Priority to TW087111259A priority patent/TW466269B/en
Priority to CO98039227A priority patent/CO5050398A1/en
Priority to US09/114,605 priority patent/US6063146A/en
Publication of DE19730085A1 publication Critical patent/DE19730085A1/en
Priority to NO20000165A priority patent/NO316403B1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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    • C—CHEMISTRY; METALLURGY
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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to crude oils and products derived therefrom containing asphalt dispersants in the form of ether carboxylic acids of general formula RO(CH2CHR1O)x(CH2CHR2O)yCH2-CO2H, wherein the substituents have the meanings given in the description.

Description

Asphaltene sind Bestandteile von Rohölen. Sie enthalten eine Vielzahl von Strukturen besonders hochmolekulare kondensierte aromatische Komponenten mit Heteroatomen. Angesichts der Komplexität ihrer Chemie werden Asphaltene als die Ölfraktion beschreiben, die in Benzol, aber nicht in n-Pentan löslich ist.Asphaltenes are components of crude oils. They contain a variety of structures particularly high molecular weight condensed aromatic components with heteroatoms. Given the complexity of their chemistry, asphaltenes are considered the oil fraction describe that is soluble in benzene, but not in n-pentane.

Im Rohöl liegen Asphaltene normalerweise als kolloidale Dispersion vor. Diese wird durch Ölharze stabilisiert.Asphaltenes are usually present in the crude oil as a colloidal dispersion. This will stabilized by oil resins.

Asphaltene können während der Produktion, der Raffination, des Transports und der Lagerung von Rohöl und davon abgeleiteten Produkten, wie z. B. schweres Heizöl oder Schiffsöl, ausfallen. Gemeinsame Ursachen für dieses Ausfallen sind ein Absinken der Temperatur oder ein Wechsel in der Zusammensetzung (z. B. Verdampfung von leicht flüchtigen Bestandteilen). Asphaltene können auch beim Fließen durch poröse Medien ausfallen. Fluten mit CO2 während des Förderprozesses kann Asphaltene zum Flokkulieren oder zum Ausfallen bringen.Asphaltenes can during the production, refining, transportation and storage of crude oil and derived products, such as. B. heavy fuel oil or marine oil fail. Common causes of this failure are a drop in temperature or a change in the composition (e.g. evaporation of volatile components). Asphaltenes can also fail when flowing through porous media. Flooding with CO 2 during the production process can cause asphaltenes to flocculate or fail.

Manche Öle enthalten Kohlenwasserstoffwachse, die bei niedrigen Temperaturen ausfallen. Wechselwirkungen zwischen dem Ausfallen von Wachs und Asphaltenen können die Gesamtmenge an ausgefallener Substanz oder deren Bildungsgeschwindigkeit erhöhen.Some oils contain hydrocarbon waxes that operate at low temperatures fail. Interactions between the loss of wax and asphaltenes can be the total amount of precipitated substance or its Increase the rate of education.

Ausgefallene Asphaltene verursachen Probleme bei der Produktion und bei der Verarbeitung von Rohölen. Asphaltene schlagen sich nieder in Ventilen, Rohren und Fördereinrichtungen. An heißen Oberflächen, wie beispielsweise Wärmetauschern, kann die Carbonisierung dieser Niederschläge ihre Entfernung sehr schwierig machen. Die Niederschläge reduzieren den Wirkungsgrad von Anlagen und können im schlimmsten Fall zu einer kompletten Blockierung und zu einem Produktionsstop führen, was hohe Kosten verursacht.Failed asphaltenes cause problems in production and in Processing of crude oils. Asphaltenes are reflected in valves, pipes and  Funding agencies. On hot surfaces, such as heat exchangers, carbonization of these precipitates can make their removal very difficult. Precipitation reduces the efficiency of plants and can worst case, a complete blockage and a production stop lead, which causes high costs.

Schweröle, die oft zum Antrieb von Schiffen verwendet werden, enthalten beträchtliche Mengen an Asphaltenen. Das Ausfallen von Asphaltenen kann sowohl zu schlechter Verbrennung als auch zu Schwierigkeiten bei der Handhabung und bei der Lagerung des Treibstoffes führen.Heavy oils, which are often used to power ships, contain considerable amounts Amounts of asphaltenes. The failure of asphaltenes can be both worse Burning as well as difficulties in handling and storage of the fuel.

Bitumen, Schweröle und Rückstände werden manchmal mit Lösemittel verdünnt, um die Viskosität für den Transport zu reduzieren. Wenn dabei Asphaltene ausfallen, so ergeben sich damit Probleme bei der Handhabung.Bitumen, heavy oils and residues are sometimes diluted with solvents to reduce the viscosity for transportation. If asphaltenes fail, so this results in handling problems.

Das Ausfallen von Asphaltenen kann durch kleine Mengen an Dispergatoren verhindert oder verringert werden. Diese Substanzen zeigen einen oder mehrere der folgenden Effekte:
The precipitation of asphaltenes can be prevented or reduced by small amounts of dispersants. These substances show one or more of the following effects:

  • a) Die Menge an Niederschlag wird reduziert;a) The amount of precipitation is reduced;
  • b) der Niederschlag bildet sich langsamer;b) the precipitation is slower;
  • c) der Niederschlag ist feiner verteilt; undc) the precipitation is more finely divided; and
  • d) die Neigung des Niederschlages, sich auf Oberflächen abzulagern, wird reduziert.d) the tendency of precipitation to deposit on surfaces reduced.

Wenn sich bereits Niederschläge an Asphaltenen gebildet haben, können sie durch den Gebrauch von Lösemitteln entfernt werden. Die Zugabe eines Dispergators kann die Wirksamkeit dieser Lösemittel verbessern.If asphaltenes have already formed precipitates, they can pass through remove the use of solvents. The addition of a dispersant can improve the effectiveness of these solvents.

Eine Vielzahl von Asphalten-Dispergatoren sind bereits bekannt. A large number of asphaltene dispersants are already known.  

CA 2 029465 und CA 2 075 749 beschreiben Alkylphenolformaldehydharze in Kombination mit hydrophilen-lipophilen Vinylpolymeren. Die Asphalten-dispergierenden Eigenschaften von Dodecylbenzolsulfonsäure wurden beschrieben in US 4 414 035, außerdem durch D.-L. Chang und H.S. Fogler (SPE paper No. 25185,1993) und durch M.N. Bouts et al. (J. pet. Technol. 47, 782-7, 1995).CA 2 029465 and CA 2 075 749 describe alkylphenol formaldehyde resins in Combination with hydrophilic-lipophilic vinyl polymers. The asphaltene-dispersing Properties of dodecylbenzenesulfonic acid have been described in US 4,414,035, also by D.-L. Chang and H.S. Fogler (SPE paper No. 25185,1993) and by M.N. Bouts et al. (J. pet. Technol. 47, 782-7, 1995).

Die bisher bekannten Dispergatoren können die durch das Ausfallen von Asphaltenen verursachten Probleme nur teilweise lösen. Da Öle in ihrer Zusammensetzung variieren, können einzelne Dispergatoren nur in einem beschränkten Bereich wirksam arbeiten. Manchmal haben sogar kleine Änderungen in der Ölzusammensetzung einen großen Effekt auf die Dispergiereigenschaften für Asphaltene. Deshalb sind in einigen Fällen die bekannten Dispergatoren nicht zufriedenstellend und zusätzliche Typen sind erforderlich.The dispersants known hitherto can be caused by the precipitation of asphaltenes only partially solve the problems caused. Because oils in their composition vary, individual dispersants can only be effective in a limited range work. Sometimes even small changes in the oil composition have one great effect on the dispersing properties for asphaltenes. That is why in some Cases the known dispersants are unsatisfactory and additional types required.

Es bestand somit die Aufgabe, neue Asphalten-Dispergatoren zur Verfügung zu stellen, die die beschriebenen Nachteile der bisher bekannten Dispergatoren nicht aufweisen.The task was therefore to provide new asphaltene dispersants do not have the described disadvantages of the previously known dispersants exhibit.

Überraschenderweise wurde gefunden, daß Ethercarbonsäuren der Formel
Surprisingly, it was found that ether carboxylic acids of the formula

RO(CH2CHR1O)x(CH2CHR2O)yCH2CO2H
RO (CH 2 CHR 1 O) x (CH 2 CHR 2 O) y CH 2 CO 2 H

verwendet werden können, um das Ausfallen und/oder das Ablagern von Asphaltenen in Rohölen und davon abgeleiteten Produkten zu verhindern.can be used to prevent the precipitation and / or deposition of asphaltenes in crude oils and products derived from them.

Gegenstand der Erfindung sind somit Rohöle und davon abgeleitete Produkte enthaltend als Asphaltendispergator Ethercarbonsäuren der Formel
The invention thus relates to crude oils and products derived therefrom containing ether carboxylic acids of the formula as asphaltene dispersant

RO(CH2CHR1O)x(CH2CHR2O)yCH2CO2H
RO (CH 2 CHR 1 O) x (CH 2 CHR 2 O) y CH 2 CO 2 H

worin
R C6-C22-, vorzugsweise C9-C18-Alkyl oder -Alkenyl, C6-C20-Alkylaryl,
R1 und R2 unabhängig voneinander H oder Methyl, vorzugsweise H bedeuten, und
x und y unabhängig voneinander eine Zahl von 0 bis 20 sind, wobei die Summe aus x und y 1 bis 20, vorzugsweise 1,5 bis 8 beträgt. wherein
RC 6 -C 22 -, preferably C 9 -C 18 alkyl or alkenyl, C 6 -C 20 alkylaryl,
R 1 and R 2 independently of one another are H or methyl, preferably H, and
x and y are independently a number from 0 to 20, the sum of x and y being 1 to 20, preferably 1.5 to 8.

Von Rohölen abgeleitete Produkte sind beispielsweise schweres Heizöl, Schiffsöl oder Bitumen.Products derived from crude oils are, for example, heavy heating oil, marine oil or Bitumen.

Die erfindungsgemäßen Ethercarbonsäuren können neben anderen Methoden durch Umsetzung von Alkylphenol oder von Fettalkoholen natürlichen oder synthetischen Ursprungs mit Ethylenoxid und/oder Propylenoxid zu den entsprechenden oxalkylierten Alkoholen und anschließender Reaktion mit Alkali (Natriumhydroxid, Kaliumhydroxid) und Natriumchloracetat bzw. Chloressigsäurederivaten hergestellt werden; zur Isolierung der Ethercarbonsäuren wird anschließend angesäuert und die Ethercarbonsäure von der salzhaltigen Wasserphase getrennt.The ether carboxylic acids according to the invention can be used in addition to other methods Implementation of alkylphenol or of fatty alcohols natural or synthetic Origin with ethylene oxide and / or propylene oxide to the corresponding oxalkylated Alcohols and subsequent reaction with alkali (sodium hydroxide, potassium hydroxide) and sodium chloroacetate or chloroacetic acid derivatives; to Isolation of the ether carboxylic acids is then acidified and the Ether carboxylic acid separated from the saline water phase.

Die so erhaltenen Produkte sind Mischungen von Molekülen mit verschiedenen Längen der Polyalkylenoxidketten. Die Zahlen x und y sind deshalb als Mittelwerte zu verstehen.The products thus obtained are mixtures of molecules with different lengths of the polyalkylene oxide chains. The numbers x and y are therefore too averages understand.

Geeignet für die Dispergierung von Asphaltenen sind sowohl reine Ethercarbonsäuren als auch deren technische Qualitäten, die neben Ethercarbonsäuren (in Anteilen < 50%, bevorzugt 60-90%) meist noch den zugrundeliegenden oxalkylierten Alkohol (in Anteilen von 1-40%, bevorzugt 5-30%) und Wasser (in Anteilen < 20%, bevorzugt 2-10%) enthalten. Bei den in den Beispielen genannten Ethercarbonsäuren handelt es sich um solche technische Qualitäten, die zwischen 60 und 80% reine Ethercarbonsäure enthalten.Both pure ether carboxylic acids are suitable for dispersing asphaltenes as well as their technical qualities, which in addition to ether carboxylic acids (in proportions <50%, preferably 60-90%) mostly the underlying alkoxylated alcohol (in Proportions of 1-40%, preferably 5-30%) and water (in proportions <20%, preferably 2-10%) contain. The ether carboxylic acids mentioned in the examples are technical qualities that are between 60 and 80% pure Contain ether carboxylic acid.

Der erfindungsgemäße Dispergator wird in einer Konzentration von 0,5 bis 10.000 ppm, vorzugsweise von 2 bis 2.000 ppm eingesetzt.The dispersant according to the invention is used in a concentration of 0.5 to 10,000 ppm, preferably from 2 to 2,000 ppm.

Zur leichteren Dosierung kann der Dispergator als Lösung in einem ölmischbaren Lösemittel formuliert werden, wie beispielsweise aromatische Kohlenwasserstoffe oder Mischungen von Kohlenwasserstoffen und einem aliphatischen Alkohol. For easier dosing, the dispersant can be used as a solution in an oil-miscible Solvents are formulated, such as aromatic hydrocarbons or Mixtures of hydrocarbons and an aliphatic alcohol.  

Zusätzlich zu dem erfindungsgemäßen Dispergator können auch Alkylphenolformaldehydharze, oxalkierte Amine, Wachsdispergatoren oder beliebige Mischungen daraus verwendet werden. Ebenfalls können andere organische Säuren mit Tensideigenschaften wie z. B. Mono- oder Dialkylbenzolsulfonsäuren, Petrolsulfonsäuren und Alkansulfonsäuren als zusätzliche Komponenten eingesetzt werden.In addition to the dispersant according to the invention can also Alkylphenol formaldehyde resins, oxalated amines, wax dispersants or any Mixtures of these are used. Other organic acids can also be used with surfactant properties such as B. mono- or dialkylbenzenesulfonic acids, Petroleum sulfonic acids and alkane sulfonic acids are used as additional components become.

Prüfung der Wirksamkeit von AsphaltendispergatorenTesting the effectiveness of asphalt dispersers Prinzip des DispergiertestesPrinciple of the dispersion test

Die Dispergierung, das Ausfällen von Asphaltenen hängt von der Natur des Kohlenwasserstoffmediums ab. Asphaltene sind in aromatischen, aber nicht in aliphatischen Kohlenwasserstoffen löslich. Somit können Dispergatoren getestet werden, indem man das Öl oder extrahierte Asphaltene in einem aromatischen Lösemittel löst und indem man dann einen aliphatischen Kohlenwasserstoff zugibt, um einen Niederschlag zu erzeugen. Da Asphaltene von dunkler Farbe sind, kann das Ausmaß des Niederschlages durch eine kolorimetrische Messung der überstehenden Flüssigkeit bestimmt werden. Je dunkler die überstehende Flüssigkeit ist, desto mehr Asphaltene bleiben dispergiert, d. h. umso besser ist der Dispergator. Dieser Test wird beschrieben in CA 2 029 465. In unserer Version des Tests wird das Fällungsmedium so ausgewählt, daß die Asphaltene zum größten Teil, aber nicht komplett ausfallen.The dispersion, the precipitation of asphaltenes depends on the nature of the Hydrocarbon medium. Asphaltenes are aromatic but not in aliphatic hydrocarbons soluble. Thus dispersants can be tested by extracting the oil or extracted asphaltenes in an aromatic Solves solvent and then by adding an aliphatic hydrocarbon to produce a precipitation. Since asphaltenes are dark in color, this can Extent of the precipitation by a colorimetric measurement of the supernatants Liquid can be determined. The darker the supernatant, the more Asphaltenes remain dispersed, i.e. H. the better the dispersant. This test will described in CA 2 029 465. In our version of the test the precipitation medium selected so that most of the asphaltenes fail, but not completely.

Vorschrift DispergiertestRegulation dispersion test

  • a) Eine 25%ige Öl-Lösung in Toluol wird filtriert, um Verunreinigungen zu beseitigen;a) A 25% oil solution in toluene is filtered to remove impurities remove;
  • b) 9,5 ml Heptan als Fällungsmittel für Asphaltene und 0,5 ml Toluol/Dispergator-Mischung (25 : 1) in ein gut 10 ml fassendes graduiertes Glasröhrchen vorlegen und gut schütteln. Dies entspricht einer Dispergatorkonzentration von 2000 ppm.
    Bei Bedarf kann die Menge Dispergator variiert werden. Für die Nullproben wird reines Toluol verwendet;    b) Place 9.5 ml of heptane as a precipitant for asphaltenes and 0.5 ml of toluene / dispersant mixture (25: 1) in a 10 ml graduated glass tube and shake well. This corresponds to a dispersant concentration of 2000 ppm.
    If necessary, the amount of dispersant can be varied. Pure toluene is used for the blank samples;
  • c) in das Glasröhrchen wird dann 0,1 ml von der gefilterten Öl-Lösung dazugegeben und ebenfalls gut geschüttelt;c) 0.1 ml of the filtered oil solution is then in the glass tube added and also shaken well;
  • d) das Ganze 2 Stunden ohne Erschütterungen stehenlassen. Die ausgefällten Asphaltene sollen sich am Boden des Röhrchens sammeln können;d) leave the whole thing for 2 hours without vibrations. The precipitated Asphaltenes should be able to collect on the bottom of the tube;
  • e) nach Ablauf dieser Zeit wird das Volumen des Sediments an Hand der Graduierung abgeschätzt, das Aussehen der gesamten Probe protokolliert und dann wird von der überständigen Phase 1 ml vorsichtig mit einer Pipette aufgenommen;e) after this time the volume of the sediment is determined using the Graduation estimated, the appearance of the entire specimen recorded and then carefully remove 1 ml of the remaining phase with a pipette recorded;
  • f) die abgesaugte Menge wird in 5 ml einer 99 : 1 Toluol-Triethanolamin-Mischung gelöst und bei 600 nm photometriert.f) the amount sucked off is in 5 ml of a 99: 1 toluene-triethanolamine mixture solved and photometrized at 600 nm.
Bewertung des DispergiertestsEvaluation of the dispersion test

Als relatives Maß für die Dispergierung wird folgender Ausdruck genommen
The following expression is taken as a relative measure of the dispersion

A = 100 (D-D0)/D0,
A = 100 (DD 0 ) / D 0 ,

wobei D und D0 optische Dichte von Meßlösung und Blindprobe sind. Der maximal erreichbare Wert von A, Amax, entspricht vollständiger Dispergierung der Asphaltene. Sie kann abgeschätzt werden, indem ein Versuch ohne Dispergator, mit Toluol anstatt Heptan, durchgeführt wird - dadurch bleiben die Asphaltene vollständig dispergiert. Das Volumen des Sediments liefert eine weitere Information über die Wirksamkeit des Dispergators. Je kleiner die Menge an Sediment ist, desto besser dispergiert ist die Substanz.where D and D 0 are the optical density of the measurement solution and blank. The maximum achievable value of A, A max corresponds to complete dispersion of the asphaltenes. It can be estimated by carrying out a test without a disperser, using toluene instead of heptane - this keeps the asphaltenes completely dispersed. The volume of the sediment provides further information about the effectiveness of the dispersant. The smaller the amount of sediment, the better dispersed the substance.

BeispieleExamples

Mit einem asphaltenreichen Öl aus Venezuela wurden erfindungsgemäße Substanzen mit dem Dispergiertest geprüft. Die Dosis betrug 2000 ppm.With an asphaltene-rich oil from Venezuela substances according to the invention were checked with the dispersion test. The dose was 2000 ppm.

Bei dieser Versuchsreihe betrug die maximale Dispergierwirkung Amax ca. 120%.In this series of tests, the maximum dispersing action A max was approximately 120%.

Claims (5)

1. Rohöle und davon abgeleitete Produkte, enthaltend als Asphalten-Dispergator Ethercarbonsäuren der allgemeinen Formel
RO(CH2CHR1O)x(CH2CHR2O)yCH2-CO2H
worin
R C6-C22-Alkyl oder -Alkenyl, C6-C20-Alkylaryl,
R1 und R2 unabhängig voneinander H oder Methyl bedeuten, und
x und y unabhängig voneinander eine Zahl von 0 bis 20 sind, wobei die Summe aus x und y 1 bis 20 beträgt.1. Crude oils and products derived therefrom, containing as asphaltene dispersant ether carboxylic acids of the general formula
RO (CH 2 CHR 1 O) x (CH 2 CHR 2 O) y CH 2 -CO 2 H
wherein
RC 6 -C 22 alkyl or alkenyl, C 6 -C 20 alkylaryl,
R 1 and R 2 independently of one another are H or methyl, and
x and y are independently a number from 0 to 20, the sum of x and y being 1 to 20. 2. Rohöle gemäß Anspruch 1, dadurch gekennzeichnet, daß
R C9-C18-Alkyl oder -Alkenyl, C6-C20-Alkylaryl,
R1 und R2 H und
x und y unabhängig voneinander eine Zahl von 0 bis 20 sind, wobei die Summe aus x und y 1,5 bis 8 beträgt.2. Crude oils according to claim 1, characterized in that
RC 9 -C 18 alkyl or alkenyl, C 6 -C 20 alkylaryl,
R 1 and R 2 H and
x and y are independently a number from 0 to 20, the sum of x and y being 1.5 to 8. 3. Verwendung von Ethercarbonsäuren gemäß Anspruch 1 als Asphalten-Dispergatoren in Rohölen und davon abgeleiteten Produkten.3. Use of ether carboxylic acids according to claim 1 as asphaltene dispersants in crude oils and derived products. 4. Verfahren zum Dispergieren von Asphaltenen in Rohölen und davon abgeleiteten Produkten, dadurch gekennzeichnet, daß Ethercarbonsäuren gemäß Anspruch 1 in einer Menge von 0,5 bis 10.000, vorzugsweise von 2 bis 2.000 ppm zugegeben werden.4. Process for dispersing asphaltenes in crude oils and the like derived products, characterized in that ether carboxylic acids according to claim 1 in an amount of 0.5 to 10,000, preferably from 2 to 2,000 ppm can be added. 5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß zusätzlich Alkylpenolformaldehydharze, oxalkierte Amine, Mono- oder Dialkylsulfonsäuren, Petrolsulfonsäuren, Alkansulfonsäuren, Wachsdispergator oder beliebige Mischungen daraus verwendet werden.5. The method according to claim 4, characterized in that in addition Alkylpenolformaldehyde resins, oxalated amines, mono- or dialkylsulfonic acids, Petroleum sulfonic acids, alkane sulfonic acids, wax dispersants or any Mixtures of these are used.
DE19730085A 1997-07-14 1997-07-14 Ether carboxylic acids as asphaltene dispersants in crude oils Withdrawn DE19730085A1 (en)

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DE19730085A DE19730085A1 (en) 1997-07-14 1997-07-14 Ether carboxylic acids as asphaltene dispersants in crude oils
PCT/EP1998/004158 WO1999004138A1 (en) 1997-07-14 1998-07-06 Ether carboxylic acids as asphalt dispersants in crude oils
EP98939618A EP0995012B1 (en) 1997-07-14 1998-07-06 Ether carboxylic acids as asphalt dispersants in crude oils
IDW20000011A ID24250A (en) 1997-07-14 1998-07-06 CARBOXICATE ESTER ACIDS AS ASPHALT DISCIPLATION IN CRUDE OILS
BR9811691-6A BR9811691A (en) 1997-07-14 1998-07-06 ether-carboxylic acids as dispersants of asphaltenes in crude oils.
CN98807194A CN1263581A (en) 1997-07-14 1998-07-06 Ether carboxylic acids as asphalt dispersants in crude oils
DE59800567T DE59800567D1 (en) 1997-07-14 1998-07-06 ETHERCARBOXYLIC ACIDS AS ASPHALT DISPERGERS IN RAW OILS
TW087111259A TW466269B (en) 1997-07-14 1998-07-10 Ethercarboxylic acids as asphaltene dispersants in crude oils
CO98039227A CO5050398A1 (en) 1997-07-14 1998-07-10 ETER-CARBOXILIC ACIDS AS DISPENSANTS OF ASPHALTENS IN OILS AND PROCEDURE FOR DISPENSING SUCH ASPHALTENS
US09/114,605 US6063146A (en) 1997-07-14 1998-07-13 Ethercarboxylic acids as asphaltene dispersants in crude oils
NO20000165A NO316403B1 (en) 1997-07-14 2000-01-12 Crude oils and derived products, use of ether carboxylic acid as asphalt dispersant and a process for dispersing asphaltenes

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